Ground- and excited-state structures of the bimetallic, ligand-bridged compound Ir-2(dimen)(4)(2+). are investigated in acetonitrile by means of time-resolved X-ray scattering. Following excitation by 2 Ps laser pulses at 390 nm, analysis of difference scattering patterns obtained at eight different time delays from 250 Ps to 300 ns yields a triplet excited-state distance between the two Jr atoms of 2.90(2) A angstrom and a triplet excited-state lifetime of 410(70) ns. A model incorporating the presence of two ground-state structures differing in Jr Jr separation is demonstrated to fit the obtained data very well, in agreement with previous spectroscopic investigations. Two ground-state isomers with Ir-Ir separations of 3.60(9) and 4.3(1) angstrom are found to contribute equally to the difference scattering signal at short time delays. Further studies demonstrate the feasibility of increasing the effective time resolution from the similar to 100 ps probe width down to the 10 ps regime by positioning the laser pump pulse at selected points in the X-ray probe pulse. This approach is used to investigate the structures of both the singlet and the triplet excited states of Ir-2(dimen)(4)(2+). 6 5